Conversion of Glucosamine to Galactosamine and Allosamine Derivatives
J . Org. Chem., Vol. 66, No. 15, 2001 5105
NMR (75 MHz, CDCl3) 38.3, 52.0, 56.9, 61.9, 68.1, 70.9, 73.1,
99.2, 123.3, 123.4, 128.3, 128.6, 129.3, 129.6, 129.9, 131.5,
133.1, 133.7, 134.1, 165.6, 165.8. HRMS (TOF) calcd for
10H, m, 10 × Ar-H. 13C NMR (75 MHz, CDCl3): 38.4, 38.9,
53.9, 55.5, 62.2, 67.2, 67.8, 73.5, 77.7, 98.3, 128.3, 128.4, 128.6,
129.5, 129.6, 133.0, 135.9, 155.6, 165.9. HRMS (TOF): calcd
for C25H32NO12S2 (M + H)+ 588.1209, found 588.1198.
C
30H31N2O11S (M + NH4)+ 627.1649, found 627.1629.
Meth yl 2-Aceta m id o-2-d eoxy-3,6-bis-(O-ben zoyl)-4-(O-
Meth yl 2-Aceta m id o-2-d eoxy-3,5-bis-(O-ben zoyl)-4-(O-
m eth a n esu lfon yl)-â-D-a llop yr a n osid e (28). Procedure as
for compound 7. Scale: 0.628 mmol. Product 28: purified by
flash chromatography and elution with 50-100% EtOAc in
hexane to give a pale yellow oil, 140 mg (43%). Rf (3:1 EtOAc/
m eth a n esu lfon yl)-r-D-a llop yr a n osid e (22). Procedure as
for compound 7. Scale: 1.26 mmol. Product 22: purified by
flash chromatography and elution with 0-1% MeOH in EtOAc
1
to give a brown gum, 210 mg (32%). ES-MS: 522 (MH)+. H
hexane): 0.47. ES-MS: 522 (MH)+, 539 (M + NH4) +, 548 (M
NMR (500 MHz, CDCl3): 2.03, 3H, s, Ac; 3.06, 3H, s, SMe;
3.41, 3H, s, OMe; 4.30, 1H, ddd (J 10.5, 4.1, 2.0), H5; 4.33,
1H, br dt (J 9.0, 3.6), H2; 4.40, 1H, t (J 2.9), H3; 4.53, 1H, dd
(J 12.3, 4.3), H6A; 4.68, 1H, dd (J 12.3, 2.0), H6B; 4.80, 1H, d
(J 4.1), H1; 4.82, 1H, dd (J 10.3, 3.0), H4; 6.49, 1H, d (J 9.0),
NH; 7.40-7.58 and 8.03-8.06, 10H, m, 10 × Ar-H. 13C NMR
(75 MHz, CDCl3): 22.9, 38.7, 49.0, 56.1, 62.5, 62.6, 68.9, 74.3,
98.7, 128.4, 128.5, 128.6, 132.9, 133.0, 133.2, 166.1, 170.0.
HRMS (TOF): calcd for C24H28NO10S (M + H)+ 522.1434,
found 522.1414.
+
+ Na)
.
1H NMR (500 MHz, CDCl3): 1.93, 3H, s, Ac; 3.03,
3H, s, SMe; 3.51, 3H, s, OMe; 4.30-4.36, 1H, m, H5; 4.41, 1H,
dt (J 3.0, 8.0), H2; 4.49, 1H, dd (J 4.4, 12.3), H6A; 4.76, 1H, dd
(J 3.0, 12.3), H6B; 4.81, 1H, d (J 7.9), H1; 5.12, 1H, dd (J 3.0,
8.9), H4; 5.96, 1H, d (J 8.1), NH; 6.04, 1H, t (J 3.0), H3; 7.43-
7.66 and 8.05-8.10, 10H, m, 10 × Ar-H. 13C NMR (75 MHz,
CDCl3): 23.0, 29.6, 38.9, 51.2, 56.3, 62.6, 69.4, 71.3, 73.1, 100.3,
128.4, 128.5, 128.9, 129.5, 129.7, 129.8, 133.2, 133.9, 165.3,
166.0, 170.0. HRMS (TOF): calcd for C24H28NO10S (M + H)+
522.1434, found 522.1436.
Meth yl
6-O-Ben zoyl-2-ben zyloxyca r bon yla m in o-2-
d e oxy-3,4-b is-(O-m e t h a n e su lfon yl)-r-D -glu cop yr a n o-
sid e (24). Procedure as for compound 7, except that compound
2313 was heated at 100 °C. Scale: 1.26 mmol. Product 24:
purified by dissolving in a small amount of EtOAc/hexane (1:
1) and filtering through a plug of silica. Evaporation of the
filtrate gave a colorless foam, 730 mg (96%). Rf (1:1 EtOAc/
hexane): 0.50. ES-MS: 588 (MH)+, 605 (M + NH4)+, 610 (M
Ack n ow led gm en t. We thank Mr. Alun J ones of the
Institute for Molecular Bioscience, U.Q., for accurate
mass measurements.
Su p p or tin g In for m a tion Ava ila ble: The detailed ex-
perimental procedures and characterization data for com-
pounds 2-6, 14-17, 20, 21, 26, and 27 and the 1H NMR
spectra of compounds 22, 24, and 28. This information is
1
+ Na)+. H NMR (300 MHz, CDCl3): 2.85, 3H, s, SMe; 3.15,
3H, s, SMe; 3.36, 3H, s, OMe; 4.06-4.20, 2H, m, H2 and H5;
4.52, 1H, dd (J 4.2, 12.4), H6A; 4.75, 1H, d (J 3.4), H1; 4.78,
1H, br d (J 12.1), H6B; 4.90, 1H, t (J 9.5), H3; 4.93, 1H, t (J
9.6), H4; 5.04, 1H, d (J 12.1), PhCHA; 5.17, 1H, d (J 12.1),
PhCHB; 5.43, 1H, d (J 9.9), NH; 7-28-7.56 and 8.06-8.09,
J O010210+